Process for the dyeing of textile material containing amino or amide groups

ABSTRACT

A process for the dyeing of textile material containing amino or amide groups, especially polyamide such as nylon is disclosed which comprises dyeing said material in a homogeneous solution of one or several water-soluble reactive dyestuffs, in a mixture of a chlorinated aliphatic hydrocarbon, especially trichloroethylene or perchloroethylene, with up to 50 percent of a hydrophilic solvent, especially N,N-dimethylformamide, during about 30 to 50 minutes at a dyeing temperature of about 40* to 130*C. The thus obtained dyeings have excellent fastness properties and the procedure is characterised in shortening the dyeing time compared with the conventional dyeing process.

United States Patent [191 Hoster et al.

[ May 20, 1975 PROCESS FOR THE DYEING OF TEXTILE MATERIAL CONTAININGAMINO OR AMIDE GROUPS [75] Inventors: I-Iansruedi Hoster, Dornach;

Branimir Milicevic, Riehen, both of [21] Appl. No.: 348,657

Related U.S. Application Data [63] Continuation of Ser. No. 124,981,March l6, 1971,

abandoned.

[52] U.S. Cl 8/54; 8/1 A; 8/1 E; 8/94; 8/163; 8/171; 8/174 [51] Int. ClD06p 3/14 [58] Field of Search 8/1 A, 54, 94, 163, 174, 8/1 E, 86, I71

[56] References Cited UNITED STATES PATENTS 3,510,243 5/l970 Seuret etal 8/39 3,556,708 l/l97l Randall 8/163 X 3,663,161 5/1972 Litzler et al.l. 8/174 3,738,803 6/1973 Blanc et al 8/174 X OTHER PUBLICATIONSMilicevic, Textile Chemists & C0l., 3/11/70, Vol. 2, No. 5, pp. 87-90and 95-98.

WAS White, Amer. Dyestuff Reporter, 7/3/67, pp. 18-23.

Primary ExaminerBenjamin R. Padgett Assistant ExaminerP. A. NelsonAttorney, Agent, or FirmWenderoth, Lind & Ponack [57] ABSTRACT A processfor the dyeing of textile material containing amino or amide groups,especially polyamide such as nylon is disclosed which comprises dyeingsaid material in a homogeneous solution of one or several water-solublereactive dyestuffs, in a mixture of a chlorinated aliphatic hydrocarbon,especially trichloroethylene or perchloroethylene, with up to 50 percentof a hydrophilic solvent, especially N,N-dimethylformamide, during about30 to 50 minutes at a dyeing temperature of about 40 to 130C. The thusobtained dyeings have excellent fastness properties and the procedure ischaracterised in shortening the dyeing time compared with theconventional dyeing process.

13 Claims, No Drawings PROCESS FOR THE DYEING OF TEXTILE MATERIALCONTAINING AMINO OR AMIDE GROUPS This is a continuation. of applicationSer. No. 124,98l, filed Mar. l6, l97l. now abandoned.

DETAILED DISCLOSURE With regard to the more stringent regulationsapplying in many places for the protection of the water againstcontamination, the dyeing of textile material using conventional methodshas the disadvantage that large quantities of water are used andsubsequently contaminated during the dyeing process. It has, therefore,already been suggested that textile materials be dyed in dye bathsprepared from organic solvents.

The present invention relates now to this problem. The object of theinvention is therefore a process for the dyeing of textile materialcontaining amino or amide groups characterised in that dyeing isperformed in a homogeneous solution of one or several dyestuffscontaining in each case at least one free sulphonic acid group and atleast one fibre-reactive group in a chlorinated aliphatic hydrocarbon,preferably boiling at a temperature of at least 70C, in a mixture withup to 50 percent of a hydrophilic solvent, preferably at the boilingpoint of the Organic mixture of solvents.

Suitable dyestuffs usable according to the invention are dyestuffscontaining not only at least one sulphonic acid group but also at leastone fibre-reactive group. The dyestuffs can belong to the most diverseclasses of dyestuffs such as to those of the mono-, disand polyazodyestuffs; of the anthraquinone, perinone, quinophthalone, oxazine,nitro, phthalocyanine, stilbene and methine dyestuffs, including thestyryl. azamethine. polymethine and azostyryl dyestuffs.

To be mentioned as fibre-reactive groupings, e.g. reactive groupingscapable of reacting with the substrate to form a covalent bond, thereare mentioned the chloromaleinylamino groups. the propiol groupings.monoand dichlorocrotonylamino groups. bromoor chloroacrylamino groups,acrylamino groups, vinyl-sulphone groups and, in particular. thegroupings containing a labile substituent, which, with accompaniment ofthe bonding electron pair, are easily split off, e.g. aliphati callybound sulphuric acid ester groups or thiosulphuric acid ester groups,and aliphatically bound sulphonyl or sulphonyloxy groups, or halogenatoms, particularly an aliphatically bound chlorine atom. These labilesubstituents are advantageously in aor B-position of an aliphaticradical which is bound by way of an aminocarbonyl or aminosulphonylgroup to the dyestuff molecule; in the case of the dyestuffs underconsideration, which contain halogen atoms as labile substituents, theseexchangeable halogen atoms can also be, e.g. in an acetyl radical, or inthe 01- or B-position of a propionyl radical. Examples of such radicalsare. e.g. chloroor oaB-dichloroor dibromopropionylamino groups, ora-chloroacetylamino groups. Preferably, however; the cleavable halogenatoms are in a heterocyclic radical preferably containing 2 to 3ring-hetero atoms, especially ring nitrogen atoms, e.g. in aphthalazine, pyridazine, pyridai'onc, quinoxaline, quinazoline, oxazole,thiazole. in particular, however, in a pyrimidine or especially triaZinering, e.g. in a grouping of the formula wherein Z represents a hydrogenatom, an optionally substituted amino group, an etherified oxy ormercapto group, or a halogen atom, or an alkyl, aryl or aralkyl group, Arepresents halogen or alkylsulphonyl and E represents hydrogen orhalogen. The halogen atoms are, e.g. fluorine or bromine atoms,preferably however, chlorine atoms. Of particular interest is the use ofdyestuffs containing the grouping of formula l halogen wherein Zrepresentsa chlorine atom, an NH -group, of the radical of an aliphaticor aromatic amine or alcohol; also such fibre-reactive groups of whichthe cleavable substituent is a quaternary ammonium or hydrazinium groupbound especially to a carbon atom of a heterocyclic radical, i.e. agroup of the formula (3 -carboxyphenylsulphonyl-l )-triazinyl-6-, 2-carboxymethylsulphonylpyrimidinyl-4-, 2-methylsulphonyl-6-methyl-pyrimidinyl-4-, 2-phenylsulphonyl-6-ethyl-pyrimidinyl-4-, 2,6-bismethylsulphonyl-pyrimidinyl-6-,2,6-bismethylsulphonyl-S-chloropyrimidinyl-4-,2,4-bismethylsulphonyl-py'rimidinyl-S-sulphonyl, 2-

methylsulphonyl-pyrimidinyl-4-, pyrimidinyl-4-,2-trichloromethylsulphonyl-6-methylpyrimidinyl-4-.2-methylsulphonyl-5-chloro-6-methylpyrimi dinyl-4-,2-methylsulphonyl-5-bromo-6-methylpyrimidin'yl-4-,2-methylsulphonyl-5-chloro-6-ethylpyrimidinyl-4-,Z-methylsulphonyl-5-chloro-6- chloromethylpyrimidinyl-4-,2-methylsulphonyl-4- Z-phenylsulphonyl- 3chloro-6-methylpyrimidine-S-sulphonyl-Z-methylsulphonyl--nitro--methylpyrimidinyl-4-, 2,5,-

methylsulphonyl-S-sulphopyrimidinyl-4-,

methylsulphonyl-6-carbomethoxy-pyrimidinyl-4-, 2-

methylsulphonyl-S-carboxy-pyrimidinyl-4-, 2-methylsulphonyl-S-cyano-6-methoxy-pyrimidinyl-4-,

2-methylsulphonyl-5-chlor0pyrimidinyl-4-, 2-sulphoethylsulphonyl-6-methyl-pyrimidinyl-4-, 2-methylsulphonyl-S-bromopyrimidinyl-4-. 2-phenylsulphonyl-S-chloropyrimidinyl-4-,Z-carboxymethylsulphonyl-S-chloro-6-methyl-pyrimidinyl-4-, 2-methylsulphonyl-6-chloropyrimidine-4- and -5- carbonyl,2,6-bis-(methylsulphonyl)-pyrimidine-4- or -5-carbonyl,2-ethylsulphonyl-o-chloropyrimidine-5- carbonyl, 2,4-bis-(methylsulphonyl )-pyrimidine-5- sulphonyl,2-methylsulphonyl-4-chloro-o-methylpyrimidine-S-sulphonyl or -carbonyl,2,4-dichloro-5- fluoro-pyrimidine-6-yl, 2-chlorobenZothiazole-5- or -6-carbonyl or -5- or -6-sulphonyl, 2-arylsulphonylor 2-alkylsulphonylbenzothiazole-S- or -6-carbonyl or -5- or -6-sulphonylradical, such as Z-methylsulphonylor 2- ethylsulphonylbenzothiazole-S-or -6-sulphonyl, or -carbonyl, 2-phenylsulphonylbenzothiazole-5- or -6-sulphonyl or carbonyl radical, and the corresponding derivatives of2-sulphonylbenzothiazole-S- or -6- carbonyl or sulphonyl radical,containing on the condensed benzene ring sulpho groups such as2-chlorobenzothioazole-S- or -6-carbonyl or -sulphonyl,Z-chlorobenzimidazole-S- or -6 -carbonyl or -sulphony],2-chloro-l-methylbenzimidazole-5- or -6- carbonyl or -sulphonyl,2-chloro-4-methylthiazole- (l 3)-5-carbonyl or -4- or -5-sulphonylradicals, and the N-oxide of the chloroor 4-nitroquinoline-5- carbonylradical. Also mentioned are the 2,2,33- tetrafluorocyclobutanecarbonyllor -sulphonyll 2-fluoro-2-chloro-3 ,3-difluorocyclobutanel -carbonyl andB-(2,2,3,3-tetrafluorocyclobutyl-l )-acryloyl, ozor 4 stated aliphaticacylamino radicals. e.g. acrylic acid, propiolic acid, chloromaleicacid, chloroacrylic acid, a,B-dibromopropionic acid, ,B-chloropropionicacid, etc., particularly, however, the halides corresponding 5 to theheterocyclic reactive radicals.

Particularly preferred are such dyestuffs containing reactiveheterocyclic groups with at least two hetero atoms such ashalogentriazinyl radicals carrying phenoxy, alkoxy, alkoxy-alkoxy orarylamino radicals, 10 those containing heterocyclic radicals havingsulphonyl groups splitting off, and those containing fluorinecontainingheterocycles, especially fluorine-containing pyrimidyl radicals as wellas dyestuffs containing as reactive grouping halogenated C fatty acids.

Examples of such dyestuffs which can be used according to the inventionare:

o a H l so Na ll l O NH N u-c c-cl ll va N -so a o ca ca o-so -oaB-bromoacryloyl and aor B-alkylor arylsulphonylacso ryloyl radicals. l-/C1 3 The dyestuffs to be used according to the invention CH areknown inappreciable numbers. The dyestuffs can 3 be prpoduced by the usualmethods, e.g. by acylation of dyestuffs containing primary or secondaryamino groups, the dyeings being of the most diverse classes as HO Sstated, especially, however, of the anthraquinone, 3 IN phthalocyanine,or azo series, using acylating agents N=N containing one or severalreactive groups. Mentioned HO S i 7 I H as such acylating agents are,e.g. the anhydrides or chlorides of the acids corresponding to the above3 9 I 4N HO S----- C I l 3 I Q so mi C N N C 1 x N fcu' N Nil-C -c-ct cN N c 3 H0.s i l 1 w I SOZNH 9 k 2 30 H OH Suitable heavy metals aremanganese, iron, and, preferably, chromium. cobalt, nickel and. inparticular, N PP l -C c-cl Such dyestuff complexes are derivedpreferably from 03 1:} 5 such azo dyestuffs which contain a group of thefor- 0 Q mulkl C I Cl x Y as well as m N N SO- H a0 I ia-R m N=N l 15wherein O and Y are each hydroxyl groups, carboxyl groups. 3 ammogroups, or alkylsulphonylamino groups. Also suitable, however, aredyestuffs of the phthalocyanine wherein R is a group of the formulaeseries.

"W 01 T Cl l N NH -CO l N Cl N}, \S 01/ l /N C1 C1 It is moreoverpossible to use fibre-reactive dyestuffs 4O Mentioned as examples ofsuitable fibre-reactive metal complexes containing sulphonic acid groupsare having sulpho groups and which contain heavy metals complexes suchas, e.g.:

in a complex bond.

no 5 on iio' c1 l 2-chromium complex 7 OH H N 1:1-chr0mium complex NH 7a 2 Ji Cl fl fl C H CO NH B so H C1 -Cu-O 5.0 I so H 36 a s 3 c u -c1 SOll 3 The mlxture of organic solvent used according to the 3 O CU Qinvention consists of a chlorinated aliphatic hydrocar- NH-CO N\/Cl bonand a hydrophilic solvent. U As chlorinated aliphatic hydrocarbons areused car- OH S0 H bon tetrachloride, chloroform, methylene chloride,trichloroethane, tetrachloroethane, dibromoethylene and, in particular,trichloroethylene and perchloroeth- COCH ylene. I

' 1 :As hydrophilic solvents which are miscible with ().Cu water areused, e.g. aliphatic alcohols such as metha- O H nol,.ethanol,n-propanol, isopropanol, ketones such as 3 acetone, methyl ethyl ketone,cyclohexanone, ether and acetals such as diisopropyl ether, diphenyleneox- HO S-OCH -CH -SO N i ide, dioxane, tetrahydrofuran glycerinformaland glycolformal, as well as acetonitrile and pyridine, diace- 3 tonealcohol, also higher-boiling glycol derivatives such as ethylene glycolmonomethyl, -ethyl and -butyl ether C1 c1 and diethylene glycolmonomethyl or -ethyl ether and so H diethylene glycol monomethyl or-ethyl ether, thiodil- :P-NH O-Cu 0 3 glycol, ethylene carbonate,'y-butyrolacton, and particl i ularly the group of the water-miscibleaprotic hydro- N=N l philic solvents boiling above C such as N,N-dime- NH thylformamide, N,N-dimethylacetamide, N-hexame- 3 thylphosphoric acidtriamide, N-methylpyrrolidone,

9 1,5-dimethylpyrrolidone. N,N-dimethylmethoxyacetamide,N,N,N,N'-tetramethylurea, tetramethyleneurea, tetramethylenesulphone(sulpholane 3- methylsulpholane and dimethylsulphoxide.

Preferred mixtures of these solvents contain 98 to 60, preferably 97 to70, per cent by weight of halogenated aliphatic hydrocarbon, and 2 to40, preferably 3 to 30, per cent by weight of hydrophilic components.

In especially preferred mixtures of solvents are used as chlorinatedaliphatic hydrocarbons trichloroethylene or perchloroethylene inadmixture with a hydrophilic solvent or the amide or lactam of a lowerfatty acid, especially N.N-dimethylacetamide or N,N-dimethylformamide orphosphorous containing solvents such as N-hexamethylphosphoric acidtriamide in admixture with a chlorinated aliphatic hydrocarbon.Efficient mixtures of solvents consist of perchloroethylene-/N,N-dimethylformamide; trichloroethylene/N,N- dimethylformamide,perchloroethylene/N,N- dimethylacetamide andperchloroethylene/N-hexamethylphosphoric acid triamide.

The present dyeing process is suitable for dyeing of textile materialcontaining amino and amide groups, e.g. certain modacrylic fibres, suchas polypropylenes modified with amines, modified polyester fibrescontaining amino groups, and, preferably, synthetic polyamides,especially poly(hexamethylene-adipic acid amide) or Nylon 6.6,(poly-(w-caprolactam) or Nylon 6, poly(hexamethylenesebacic acid amide)or Nylon 6.10 or poly( l l-aminoundecanoic acid) or Nylon 11 as well asnatural polyamides such as wool.

In exhaust dyeing, the textile material to be dyed can be in the form ofloose material, fleece, yarn, or as knitted goods or fabrics. It isdyed, in loose form or in a form achieved by mechanical means, in astationary bath, especially in suitable dye-jigs, winch-vats,cheesedyeing machines, or similar dyeing-machines, depending on thenature of the material to be dyed.

The dyeing may be performed in dyeing apparatus or dyeing vessels whichare linked with the outside atmosphere (if necessary via a refluxcondenser), or in closed vessels, such as pressure vessels. with orwithout pressure.

Dyeing is performed at a temperature of about 40 to 130C, preferably ata temperature where the textile material is not injured, for examplepolyamide at about 105C. during 30 to 50 minutes.

After attainment of the desired depth of colour, the dyed material isremoved from the dye-bath and then preferably aftertreated with acommercial cleansingintensifier dissolved in, e.g. perchloroethylene.For the removal of the solvent still adhering, the textile material istreated either with steam or with hot air stream.

A further advantage of the dyeing process according to the invention isthe shortening of the dyeing time compared with the conventional dyeingprocesses.

In the following non-limitative examples, if not otherwise stated, theterm parts denotes parts by weight.

percentages are percentages by weight, and temperatures are given indegrees Centigrade.

EXAMPLE 1 03 Parts of the dyestuff of the formula are dissolved in 16parts of N,N-dimethylformamide, and diluted with 145 parts ofperchloroethylene. In this dye liquor, 5 parts of polyamide knittedfabric are dyed for 40 minutes at and then removed from the dye bath. Ofa commercial cleansing-intensifier, such as is used in chemicalcleaning, 1 to 2 parts are dissolved in 160 parts of perchloroethylene,and the dyed knitted fabric is aftertreated for 10 minutes at 50 in thisbath.

'The material is subsequently dried in a warm air stream. By this meansis obtained an even red dyeing having excellent fastness properties.

EXAMPLE 2 0.8 Parts of the dyestuff of the formula C CH EXAMPLE 3 0.2Parts of the dyestuff of the formula C 1 N W are dissolved in 19 partsof N.N-dimethylacetamide. and diluted with 288 parts ofperchloroethylene. In this dye liquor, 10 parts of polyamide 66 knittedfabric are dyed for 45 minutes at 105 and then removed from the dyebath. 1 to 2 parts of a commercial cleansingintensifier, such as is usedin dry cleaning, are dissolved in 320 parts of perchloroethylene, andthe dyed knitted fabric is aftertreated for 10 minutes at 50 in thisbath. The material is subsequently dried in a warm air stream. A levelscarlet red dyeing having good fastness properties is obtained.

Nil-G NHCOCH CI are dissolved in 19 parts of N,N-dimethylformamide, anddiluted with 288 parts of perchloroethylene. In this dye liquor, 10parts of woollen fabric are dyed for 45 minutes at 90 and then removedfrom the dye bath. 1 to 2 parts ofa commercial cleansing-intensifier,such as is used in dry cleaning, are dissolved in 320 parts ofperchloroethylene, and the dyed fabric is aftertreated for l minutes at50 in this bath. The material is subsequently dried in a warm airstream. A level blue dyeing having good fastness properties is obtained.

If the 19 parts of N,N-dimethylformamide are replaced by 15 parts ofN-hexamethyl-phosphoric acid triamide, and otherwise the procedure ofExample 4 is follwed, dyed material is obtained with similarly goodproperties.

NH l 2 son EXAMPLE 5 0.2 Parts of the dyestuff of the formula H0 9 Cl Iff wl a W H038 \N/. N N/N I: H F I\ C/ are dissolved in 19 parts ofN,N-dimethylformamide, and diluted with 288 parts of perchloroethylene.In this dye liquor, parts of polyamide 66 or woollen knitting yarn aredyed for 45 minutes at 121 and then rinsed in a new bath in pureperchloroethylene for l0 minutes at The dyed material is then dried in awarm air stream. A level blue dyeing having excellent fastnessproperties is obtained.

What we claim is:

1. A process for the dyeing of a textile material containing amino oramide groups, which consists essentially of performing the dyeing byexhaust dyeing in a homogeneous solution of one or several dyestuffs,each of said dyestuffs containing at least one free sulphonic acid groupand at least one fiber-reactive group in a solvent mixture consistingessentially of 98 to percent by weight chlorinated aliphatichydrocarbon, admixed with 2 to 50 percent by weight of a hydrophilicsolvent.

2. A process according to claim 1 wherein the dyeing is performed at theboiling point of the organic solvent mixture.

3. A process according to claim 1 wherein the mixture of organicsolvents contains 98 to 60 percent by weight of chlorinated aliphatichydrocarbon and 2 to 40 percent by weight of a hydrophilic solvent.

4. A process according to claim 1 wherein perchloroethylene is used inadmixture with a hydrophilic solvent.

5. A process according to claim 1 wherein the solvent mixture employedis the amide or lactam of a lower fatty acid, especiallyN,N-dimethylacetamide or N,N-dimethylformamide in admixture with achlorinated aliphatic hydrocarbon.

6. A process according to claim 1 wherein the mixture of solvents usedis: perchloroethylene/N,N-dimethylformamide,trichloroethylene/N,N-dimethylformamide,perchloroethylene/N,N-dimethylacetamide orperchloroethylene/N-hexamethylphosphoric acid triamide.

7. A process according to claim 1 wherein natural or synthetic polyamidematerials are dyed.

8. A process according to claim 7 wherein wool is dyed.

9. A process according to claim 7 wherein synthetic polyamide materialis dyed.

10. The dyed textile material obtained by the process of claim 1.

11. A process according to claim 3 wherein the mixture of organicsolvents contains 97 to percent by weight of chlorinated aliphatichydrocarbon and 3 to 30 percent by weight of a hydrophilic component.

12. A process according to claim 1 wherein the sulphonic acid groupscontaining dyestuffs contain as the fiber-reactive radical a radical ofa halogenated C fatty acid.

13. A process according to claim 12 wherein the chlorinated aliphatichydrocarbon is perchloroethylene and the hydrophilic solvent isN,N-dimethylformamide. l

1. A PROCESS FOR THE DYEING OF A TEXTILE MATERIAL CONTAINING AMINO ORAMIDE GROUPS, WHICH CONSISTS ESSENTIALLY OF PERFORMING THE DYEING BYEXHAUST DYEING IN A HOMOGENEOUS SOLUTION OF ONE OR SEVERAL DYESTUFFS,EACH OF SAID DYESTUFFS CONTAINING AT LEAST ONE FREE SULPHONIC ACID GROUPAND AT LEAST ONE FIBERREACTIVE GROUP IN A SOLVENT MIXTURE CONSISTINGESSENTIALLY OF 98 TO 60 PERCENT BY WEIGHT CHLORINATED ALIPHATICHYDROCARBON, ADMIXED WITH 2 TO 50 PERCENT BY WEIGHT OF A HYDROPHILLICSOLVENT.
 2. A process according to claim 1 wherein the dyeing isperformed at the boiling point of the organic solvent mixture.
 3. Aprocess according to claim 1 wherein the mixture of organic solventscontains 98 to 60 percent by weight of chlorinated aliphatic hydrocarbonand 2 to 40 percent by weight of a hydrophilic solvent.
 4. A processaccording to claim 1 wherein perchloroethylene is used in admixture witha hydrophilic solvent.
 5. A process according to claim 1 wherein thesolvent mixture employed is the amide or lactam of a lower fatty acid,especially N,N-dimethylacetamide or N,N-dimethylformamide in admixturewith a chlorinated aliphatic hydrocarbon.
 6. A process according toclaim 1 wherein the mixture of solvents used is:perchloroethylene/N,N-dimethylformamide,trichloroethylene/N,N-dimethylformamide,perchloroethylene/N,N-dimethylacetamide orperchloroethylene/N-hexamethylphosphoric acid triamide.
 7. A processaccording to claim 1 wherein natural or synthetic polyamide materialsare dyed.
 8. A process according to claim 7 wherein wool is dyed.
 9. Aprocess according to claim 7 wherein synthetic polyamide material isdyed.
 10. The dyed textile material obtained by the process of claim 11.A process according to claim 3 wherein the mixture of organic solventscontains 97 to 70 percent by weight of chlorinated aliphatic hydrocarbonand 3 to 30 percent by weight of a hydrophilic component.
 12. A processaccording to claim 1 wherein the sulphonic acid groups containingdyestuffs contain as the fiber-reactive radical a radical of ahalogenated C1-4 fatty acid.
 13. A process according to claim 12 whereinthe chlorinated aliphatic hydrocarbon is perchloroethylene and thehydrophilic solvent is N,N-dimethylformamide.